Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
  • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09J131/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/28—Non-macromolecular organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/28—Non-macromolecular organic substances
  • C08L2666/34—Oxygen-containing compounds, including ammonium and metal salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• packaging material from more than one layer, e.g. B. to coat cardboard or paper for mechanical protection with plastic films or laminate different films to each other, for example to reduce gas and / or liquid permeability.
• the adhesive used there consists of an aqueous dispersion of an ethylene-vinyl acetate copolymer (PEVAC), into which 5 to 30% by weight, based on PEVAC, epoxy resins are incorporated and to which an amine hardener is added.
• PEVAC ethylene-vinyl acetate copolymer
• the adhesive is produced, for example, by dissolving the mixture of an aqueous solution of protective colloids and sodium acetate with epoxy resin in vinyl acetate, adding ethylene and polymerization using a water-soluble redox catalyst system, and then adding polyamine.
• the object of the invention was accordingly to provide an adhesive which, after its use, gives laminates or laminated shaped structures, the improved strength of the composite, in particular also during and after thermal stress and in many cases even during and after stress by boiling water.
• the adhesive is preferably produced in such a way that on the one hand 1 part by weight of the dispersion a) with 0.1 to 40% by weight, based on the copolymer, epoxy compound of the type defined above and optionally further additives and on the other hand 0.7 to 1 3 parts by weight Dispersion a) is admixed with 0.1 to 40% by weight, based on the copolymer, amine hardener and optionally further additives, and the components thus obtained are then mixed homogeneously with one another.
• the adhesives according to the invention are outstandingly suitable for producing laminates from sheet-like structures or moldings from one or more of the following materials: polyolefins, polyesters, polyamides, vinyl and vinylidene polymers, modified cellulose.
• the materials mentioned are also understood to include those which contain mixtures of the substances mentioned, i.e. blends e.g. B. of polyamide and polyester, but also (graft) copolymers of monomer units from the group of alpha-olefins, for. B. ethylene, vinyl and vinylidene halides, e.g. B. vinyl chloride and vinylidene chloride, vinyl esters, e.g. B. vinyl acetate, vinyl propionate and vinyl laurate, alpha, betaethylenically unsaturated carboxylic acids.
• blends e.g. B. of polyamide and polyester
• graft copolymers of monomer units from the group of alpha-olefins for. B. ethylene, vinyl and vinylidene halides, e.g. B. vinyl chloride and vinylidene chloride, vinyl esters, e.g. B. vinyl acetate, vinyl propionate and vinyl laurate, alpha, betaethyl
• the adhesives according to the invention can advantageously be used to laminate paper, cardboard or metal, e.g. As aluminum and tin, use with fabrics made of the above materials.
• the above materials are particularly preferably used as flat structures, in particular as foils.
• the aqueous dispersion a) is preferably prepared by copolymerization of vinyl esters with straight or branched, preferably saturated monocarboxylic acids having 1 to about 18 carbon atoms or acrylic acid esters with alkanols having 1 to about 18 carbon atoms or mixtures of these monomers on total monomers, about 0.1 to about 10% by weight of ethylenically unsaturated monomers which have hydroxyl and carbonyl radicals as functional groups, and optionally further monomers in the presence of customary protective colloids and / or emulsifiers and preferably water-soluble initiator systems. It is also possible to add the epoxy compounds before, at the beginning or during the polymerization. However, these compounds are preferably only added after the end of the polymerization.
• the ethylenically unsaturated monomers which have hydroxyl and carbonyl radicals as functional groups are preferably mono- and dicarboxylic acids having 3 to 18 carbon atoms, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, or N-methylolacrylamide or N- Methylol methacrylamide or mixtures of these compounds are used.
• the methylol compounds mentioned are particularly preferred.
• copolymer dispersions used according to the invention are preferably produced by the known polymerization processes by emulsion polymerization, preferably with solids contents of 3 to 70% by weight, based on the total weight.
• Part of the dispersion a) is admixed with epoxy compound.
• epoxy compounds are e.g. B. those based on epichlorohydrin-bisphenol A, glycidyl ethers of polyhydric alkanols, epoxypropylamines, novolakepoxy compounds, cycloaliphatic resins, e.g. Dicyclopentadienyl dioxide, diglycidyl ester of hexahydrophthalic acid, vinyl cyclohexane dioxide, epoxy compounds of alkylphenols or of fatty acid derivatives. They generally have epoxy equivalent weights of 80 to 1000 and preferably have viscosities of 0.2 to 40 Pa ⁇ s at 25 ° C. Many of them are commercially available.
• epoxy compounds can be used as such, but it is also possible to first disperse them in water and then to use these dispersions.
• the epoxy compound is preferably added to this part of the dispersion a) in amounts of 5 to 30% by weight, based on the copolymer.
• Another part of the dispersion a) is preferably added to the amine hardener in amounts of 5 to 30% by weight, based on the copolymer.
• These hardeners are generally composed of amines and / or amides, in many cases also of polyamines and / or polyamides. Many of them are also commercially available. Examples are aliphatic polyamines, their derivatives and salts, e.g. B.
• diethylenetriamine triethylenetetramine, dimethylaminopropylamine, ethylenediamine, adducts of these compounds with mono- or polyfunctional glycidyl ethers such.
• piperidine benzyldimethylamine, dimethylaminomethylphenol, polyaminoimidazolines, polyaminoamides, e.g. B. resinous condensation products from oligomerized vegetable oils, * unsaturated fatty acids and aryl or alkyl polyamines. * z. B. tall oils,
• the two dispersions one of which contains the epoxy compound and the other of which contains the hardener, are then mixed together in a ratio of about 1: 0.7 to 1: 1.3 to form the reactive adhesive according to the invention.
• the ratio of epoxy compound and hardener is then preferably in a range from 1: 1 to 400: 1, in particular between 1: 1 and 25: 1.
• the ratio 1: 1 produces optimal results.
• the amine hardener can also be used in protective over the epoxy compound.
• the adhesive thus obtained generally has pot lives from a few hours to about 2 weeks.
• the desired pot life can easily be set by a person skilled in the art, if necessary after a few attempts.
• the adhesive obtained in this way can be used as such or else mixed with additives.
• it is desirable to set certain viscosities for example by adding water or filler.
• the optimal viscosities depend on the type of processing to be carried out.
• Adhesive dispersions with viscosities of approximately 10 to 500 mPa ⁇ s have been found to be particularly advantageous for application by means of a roller, eg B. also proven in "reverse roll coating", gravure or air brush.
• adhesives according to the invention with viscosities of up to 5000 mPa.s can be used particularly advantageously.
• the two components consisting of copolymer dispersion and epoxy compound or copolymer dispersion and amine hardener can of course also be produced from two different copolymer dispersions. In general, however, it is preferred to divide a dispersion into approximately equal parts and to add epoxy compound or hardener. At the same time or afterwards, further additives can also be added to these two components, if this is desired in order to achieve special effects.
• fillers e.g. B. finely divided silicon dioxide, carbon black or plastic powder, dyes, thixotropic agents, plasticizers and dispersing agents.
• the addition is preferably limited to up to 10% by weight, based on the solids content of the adhesive.
• no fillers or pigments are added if translucent to clearly transparent laminates are to be produced.
• the laminating and laminating adhesive according to the invention is generally applied by roller application, air brush, gravure printing, doctor blade device or spraying onto the flat structures or moldings, in particular onto the film. It has proven to be advantageous in some cases to pretreat the surface to be coated, for example by coronary discharges, ozonization, primer addition, the latter in particular in the case of metals, or the like. In general, wet film thicknesses of the adhesive of 10 to 30 ⁇ m are sufficient.
• the dispersion layer is then by convection of hot gases, for. B. hot air, dried by infrared, high frequency or another conventional drying process.
• the flat structure or the shaped body is then preferably laminated at temperatures between 60 and 100 ° C.
• a film made from the materials mentioned at the outset is connected to a further film which can differ in material from the other. * often at pressures from about 10 to about 1000 kN / m 2
• paper, cardboard (cardboard) or metal is laminated with a film made from the materials listed at the beginning with the aid of the adhesive according to the invention.
• the laminates or laminating products made using the adhesive according to the invention show have increased strength compared to the prior art, in particular during and after long-term exposure to heat and water. In contrast to the laminates produced by previous processes, such products are often even sterilisable. In many cases, the limit for the thermal, mechanical and chemical resilience is no longer set by the strength of the bond, but rather by the strength of the flat structures or moldings connected by means of the laminating and laminating adhesive according to the invention.
• the adhesive dispersions were applied with a wet film thickness of approximately 12 ⁇ m to approximately 60 ⁇ m thick polyethylene film in a width of 2 cm, dried by hot air (approximately 80 to 90 ° C.) and then with 392, 3 kN / m 2 sealed against a second polyethylene film at approx. 90 ° C. After the specified storage time, the two films are pulled apart at a speed of 300 mm / min at an angle of 180 ° over a length of 15 cm. The force required for this was measured in Newtons and given as a measure of the peel strength.
• an aqueous dispersion of a copolymer having a composition of 52% by weight of vinyl acetate, 6% by weight of butyl acrylate, 39% by weight of ethylene and 3% by weight of N-methylolacrylamide units with a solids content of 45% by weight were mixed with 18% by weight .Tl.
• the total solids content of the dispersion thus prepared was then adjusted to 40% by weight with water.
• the polyaminoimidazoline resin As a 75% by weight solution in dilute acetic acid at 25 ° C., the polyaminoimidazoline resin has a viscosity of 10 to 20 Pa ⁇ s and an amine number of 210 to 240.
• Both modified copolymer dispersions were mixed together and applied to a 60 ⁇ m thick polyethylene film in such an amount that each m 2 of film was coated with about 5 g of dry mass of the adhesive. After drying with hot air, sealing was carried out at 80 to 90 ° C. against the same polyethylene film.
• Example 1 was repeated, except that the di s -7-8 Persion with 45 wt% solids, a copolymer of 61 wt% of vinyl acetate, 7% by weight of butyl acrylate, 29 wt% ethylene and 3% by weight N- Contained methylolacrylamide units.
• Example 1 was repeated with the modification that an aqueous dispersion with a solids content of 45% by weight of a copolymer of 78% by weight of vinyl acetate and 22% by weight of ethylene was used.
• Example 1 was repeated with the modification that the starting dispersion with a solids content of 65% contained a copolymer of 96% by weight ethyl acrylate and 4% by weight N-methyl acrylamide units.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)
• Materials For Medical Uses (AREA)

Applications Claiming Priority (3)

Publications (3)

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ID=25787504

Family Applications (1)

Country Status (4)

Cited By (3)

Families Citing this family (21)

Family Cites Families (9)

• 1980
  • 1980-12-19 EP EP80108046A patent/EP0046823B1/fr not_active Expired
  • 1980-12-19 AT AT80108046T patent/ATE4727T1/de not_active IP Right Cessation
• 1981
  • 1981-05-20 US US06/265,542 patent/US4377433A/en not_active Ceased
  • 1981-05-28 CA CA000378507A patent/CA1205232A/fr not_active Expired
• 1991
  • 1991-05-06 US US07/696,189 patent/USRE34766E/en active Active

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